Dicarbamates



P Patented sepi li Examples of compounds within the scope of the inven- 3,341,568 tion include: DICARBAMATES diamyl[ (methylimino diethylene] -dicanbamate,

George E. Ham, Lake Jackson, Tex., assignor to The Dow Chemical Company, Midland, Mich, a corporation of dlethyu(cyclopentyhmmo)dlethylenfidlcarbamate Delaware 5 'ethyl-propyl (cycloheptylimino) diethylene] -d icarbamate, N0 Drawing. Filed Sept 5, 1963, sen 306,719 d octadecyl[(phenylethylnnino)drethylene1-drcarbamate,

12 Claims (CL 2 0 4 drethyl[(benzylumno)d1-1-propylene]-cl1carbamate and diethyl (n-decylimino) diethylene] -dicarbamate.

This invention relates to new nitrogen-containing com- The process of the invention may be carried out at any positions of matter which are useful as bactericides and to 10 temperature of from 25 to 150 C. (preferably from methods of preparing such compositions. More particuabout 70 to 90 C.) either with or without a suitable larly, the present invention relates to bactericidal cominert solvent. The reaction may be carried out at any pounds which contain two N-substituted alkyl carbamate pressure from a few hundredths of a millimeter of Hg groups per molecule linked by a divalent chain composed to 100 atmospheres. The mole ratio of primary amine to of carbon atoms and at least one nitrogen atom, and to aziridinyl compound may vary from 1:2 to about 5:1. the preparation of such compounds by the reaction of a When excessive amounts of amine are used, an extra primary amine and an alkyl aziridinylfonnate. separation step is generally required to separate the amine It is known that O-cyclohexyl-N,N-ethylene-urethane from the product formed. Amounts of reactants sufiicient (cyclohexyl aziridinylformate) reacts slowly with aniline to provide an aziridinyl group for each hydrogen atom at room temperature to give O-cyclohexyl-N-(B-anilinoin the primary amine (i.e., stoichiornetric amounts) ethyl)urethane, as disclosed by Iwakura et al. in J. Org. should be employed for most economical operation. For Chem. 25, 1l18l123 (1960). The compound N,N-bis example, good results are obtained by the reaction of (B-p-methylphenoxycarbonylamino)ethyl p-phenetidine ethylamine or n-propylamine and n-propyl aziridinylhas also been prepared by the reaction of O-p-tolyl-N,N- formate at temperatures of from 70 to 90 C. when the ethyleneurethane and p-phenetidine, although neither O- mole ratio of amine to aziridinyl compound is about 1:2. ethyl-N,N-ethyleneurethane nor On-hutyl-N,N-ethylene- Suitable solvents include acetonitrile, Water, alkanols urethane gave a reaction with aniline. (especially secondary and tertiary alcohols) such as i- The reaction upon which the present invention is based propanol, t-butanol, acetone, ether and inert hydrocaris represented by the equation bOIlS Such as 1361116116, toluene 0f n-hexalle- 0 0 (JRO Ro I 1' 0 YI H RNHi+2R-0( iN R'0-(" I I( 3( 3-I I(|)--oNoo-n CR. 1'1. It. R. R.

wherein each R may be the same or diflerent and is se- All of the compounds of the invention contain threelected from the group consisting of the hydrogen atom nitrogen atoms (two secondary amide groups and one and a lower alkyl group of 14 carbon atoms (preferably tertiary amine group) and in concentrated or dilute solua hydrogen atom or a methyl group), R may be a hydrotions inhibit or prevent the growth of Aerobacter aerogen atom or may be a hydrocarbyl group which contains genes. from 1 to 10 carbon atoms such as an alkyl, cy-cloalkyl The following examples are submitted for the purpose or aralkyl group and R' (which may !be the same or difof illustration only and are not to be construed as limiting ferent) is an alkyl group of from 1 to 18 carbon atoms. the scope of the invention in any way.

Example 1 CHzCHgCHzCHa O H at 2CH OHqO( JN +CH3OHiOHzCHgNH2 CHaCH2O-CN-OHaCHi-NCHiCHiNCOCHaCHa orn Suitable alkyl R and R groups include methyl, ethyl, n- Into a reaction vessel equipped with a means for stirpropyl, i-propyl, n-butyl, i-butyl, sec.-butyl, t-butyl, as well ring, temperature control and refluxing were placed 23 as n-pentyl, hexyl, heptyl, octyl, nonyl and decyl groups. grams (0.2 mole) of ethyl .aziridinylformate, 14.6 grams In addition, R may be an undecyl, dodecyl, tridecyl, 5 (0.2 mole) of n-butylamine and 150 milliliters of dry tetradecyl, pentadecyl, cetyl, heptadecyl or octadecyl aoetonitrile. This mixture was refluxed for 6 /2 hours at group. Other suitable R groups include cyclopentyl, cyclo- 80 C. and the acetonitrile was removed under reduced hexyl, methylcyclohexyl, cycloheptyl, benzyl, tolylethyl pressure. The yield was 49.4 percent of diethyl-[(n-butyl and phenylethyl groups. Unsymmetrical compounds (with imino)diethylene1dicarbamate (about .05 mole) based on different R groups) are prepared by using two diiferent ethyl aziridinylformate. The fraction which would not alkyl aziridinylformates either sequentially or as a mixdistill below 150 C. at 0.5 millimeters of Hg was identiture (for example, methyl aziridinylformate, ethyl aziridified by infrared spectroscopy as the desired compound nylformate and n-butylamine may be combined in an and was a colorless viscous liquid. equimolar mixture to form ethyl-methyl [(n-butylimino) Neutralization equivalent: Found, 303, Calculated, diethylene]dicarbamate). 303.

Example 2 Into a reaction vessel equipped with a means for stirring, temperature control and refluxing were placed 23 grams (0.2 mole) of ethyl aziridinylformate, 14.6 grams (0.2 mole) of isobutyl amine and 150 milliliters of dry acetonitrile. The mixture was refluxed for 6 hours at 80 C. and the acetonitrile was removed under reduced pressure. The yield was 49.2 percent based on ethyl aziridinylformate and the clear viscous product would not distill below 180 C. at 1.5 millimeters of Hg.

The infrared spectrum was consistent with that for diethyl[ (i-butylimino) diethylene] dicarbamate.

Neutralization equivalent: Found, 304. Calculated, 303.

Example 3 Example 4 CHQNHQ 2 CHs(CH2)12O-C-N\ Into a reaction vessel equipped with a means for stirring, temperature control and refluxing were placed 53.89 grams (0.2 mole) of tridecyl aziridinylformate, 10.72 grams (0.1 mole) of benzylamine and 50 milliliters of dry acetonitrile. The mixture was refluxed tor'three days at 85 C. and the acetonitrile was removed under reduced pressure; A 97.2 percent yield based on tridecyl aziridinylformate was obtained.

The infrared spectrum was consistent with that for di (tridecyl) (benzylimino) diethylene1dicarbamate.

Neutralization equivalent: Found, 639. Calculated, 646.

Example 5 0 CH2 H 2CHa(CH2)n0-CN\ NH:

0 H H O (S means that the ring is saturated, i.e., a cyclohexyl p) Into a reaction vessel ring, temperature control equipped wi th a means for stirand refluxing were placed 53.89

grams (0.2 mole) of tridecyl aziridinylformate, 9.92 grams (0.1 mole) of cyclohexylamine and 50 milliliters of acetonitrile. The mixture was refluxed for three days at C. and the acetonitrile was removed under reduced pressure. The yield was 97.3 percent based on tridecyl aziridinylformate of a clear viscous liquid.

The infrared spectrum was. consistent with that for di(tridecyl) (cyclohexylirnino) diethylene1dicarbamate.

Neutralization equivalent: Found, 634. Calculated, 638.

Example 6 Petri dishes containing nutrient agar were streaked with Aerobacter aerogenes. The compounds from Examples 1 through 5 were cross-streaked into the agarcontaining Petri dishes. Growth was observed for 72 hours at 25 C. No growth was observed at the intersection of the test compounds and the Aerobacter aerogenes. In all other areas, growth was abundant.

I claim as my invention:

1. A compound of the formula sisting of the hydrogen atom and a lower alkyl group, the group consisting of the hydrogen atom and a hydrocarbon group of from 1 to 10 carbon atoms selected from the group consisting of R is selected from alkyl, cycloalkyl and aralkyl groups, and each R is an alkyl group of from 1 to 18 carbon atoms.

2. A compound according to claim 1 wherein R is an ethyl group.

3. A compound according to claim 1 wherein R is a.

tridecyl group.

4. The compound diethyl[(n-butylimino)-diethylene] dicarbamate.

5. The compound diethyl[(i-butylimino)-diethylene] dicarbamate.

6. The compound dicarbamate.

7. The compound.di(tridecyl)[(benzylirnino)diethylene] dicarbamate.

diethy1[ (t-butylimino) -diethylene] 8. The compound di(tridecyl)[(cyclohexylimino)di-.

ethylene] dicarb amate.

9. A process for the preparation of a dicarbamate.

which comprises reacting:

(a) a primary amine of the formula RNH wherein R is a hydrocarbon group of from 1 to 10 carbon atoms selected from the group consisting of alkyl, cycloalkyl and aralkyl radicals, and

(b) an alkyl aziridinylformate of the formula wherein R is an alkyl group of from 1 to 18 carbon atoms and each R is independently selected.

5 6 12. The process of claim 9 wherein acetonitrile is em- OTHER REFERENCES P y asasolvent- Iwakura et al., J. Org. Chem, v01. 25 (1960) pp.

R f CT d 1118-1123.

e erences l e Coleman et al., J. Am. Chem. Soc., vol. 68 (1946) FOREIGN PATENTS 5 pp. 2006-2007. 904914 2/1945 France LORRAINE A. WEINBERGER, Primary Examiner.

925,495 3/1955 Germany.

67,192 12/1943 Norway. RICHARD K. JACKSON, Examiner. 

1. A COMPOUND OF THE FORMULA 